Hardenable mixture of substrances, production method and use thereof

ABSTRACT

A curable composition comprising  
     (A) constituents containing carbamate groups I:  
     —O—C(O)—NHR (I)  
      in which R=a hydrogen atom or an alkyl, cycloalkyl or aryl group,  
     (B) constituents containing carbamate-reactive groups, the equivalents ratio of carbamate-reactive groups in (B) to carbamate groups in (A) being &gt;0.2,  
     (C) adducts preparable from  
     (c1) polyisocyanates and  
     (c2) compounds II containing isocyanate-reactive functional groups:  
                 
 
      in which  
     R 1  and R 2 : independently of one another are hydrogen atoms or alkyl radicals;  
     X and Y: oxygen atom, sulfur atom or a radical &gt;N—R 6 , in which R 6 =aliphatic radical;  
     R 3 : is an alkylene radical;  
     R 4  and R 5 : are hydrogen atoms, isocyanate-reactive functional groups or R 6 ;  
     with the proviso that one group R 4 , R 5  or R 6  contains an isocyanate-reactive functional group or R 4  or R 5  is an isocyanate-reactive functional group and the other radicals R 4 , R 5  or R 6 —where present—contain no isocyanate-reactive groups;  
     the molar ratio of (c1) to (c2) being chosen such that the adducts (C) contain in the molecule isocyanate groups;  
     process for its preparation, and its use.

[0001] The present invention relates to a novel curable composition. Thepresent invention also relates to a novel process for preparing curablecompositions. The present invention additionally relates to the use ofthe novel curable compositions for producing moldings and films and alsoas coating materials, adhesives, and sealing compounds for producingcoatings, adhesive films, and seals.

[0002] Two-component coating materials comprising reactive componentscontaining isocyanate-reactive functional groups, customary and knownpolyisocyanates, and adducts of diisocyanates and dioxolanes, dioxanesor oxazolidines containing an isocyanate-reactive functional group, in amolar ratio of 1:1, are known from the German patent application DE 19609 617 A1.

[0003] According to page 3 line 68 to page 4 line 10, said reactivecomponents comprise, inter alia, hydroxy-functional polymers having ahydroxyl content of from 0.1 to 20% by weight (corresponding to from 33to 660 mg KOH/g). The number-average molecular weight of these polymersis preferably from 1000 to 100,000. The polymers contain preferably morethan 50% by weight of C₁-C₂₀ alkyl (meth)acrylate, vinylaromatics havingup to 20 carbon atoms, vinyl esters of carboxylic acids containing up to20 carbon atoms, vinyl halides, nonaromatic hydrocarbons having from 4to 8 carbon atoms and one or two double bonds, unsaturated nitrites, andmixtures thereof. Preferred polymers are those containing up to 60% byweight of C₁-C₁₀ alkyl (meth)acrylates, styrene or mixtures thereof.Additionally, the polymers contain in copolymerized formhydroxy-functional monomers, corresponding to the above hydroxylcontent, and also further monomers, such as unspecified unsaturatedacids, especially carboxylic acids, acid anhydrides or acid amides.According to page 9 lines 30 to 45, “Preparation and testing ofclearcoat materials with the compounds A—two-component system”, thehydroxy-functional vinyl polymer Lumitol® H 136 from BASFAktiengesellschaft is used as the reactive component, this being anacrylate copolymer of hydroxypropyl acrylate, styrene, isobutylacrylate, and acrylic acid with an OH number of 136 mg KOH/g.

[0004] The reactive components, accordingly, do not contain carbamategroups.

[0005] The known clearcoat materials have a high solids content of up to76% by weight. The clearcoats produced from them have good mechanicalproperties, particularly a high hardness and flexibility, and also highchemical resistance.

[0006] The two-component coating materials known from the German patentapplication DE 196 09 617 A1 are not, however, so broadly applicable aswould actually be desirable. Moreover, their pot life, i.e., the timewithin which they can be processed without problems after the twocomponents have been mixed, and give flawless coatings, is still in needof lengthening.

[0007] The German patent applications DE 198 50 243 A1 or DE 198 50 210A1 disclose curable compositions comprising binders that are free fromcarbamate groups. Where they are one-component systems, the compositionscomprise crosslinking agents which may, inter alia, be amino resins.Where they are multicomponent systems, it is also possible to use theisocyanato-containing adducts known from the German patent applicationDE 196 09 617 A1. The conjoint use of amino resins and the knownisocyanato-containing adducts is neither recommended nor documented byan example. As multicomponent systems, the compositions known from theGerman patent application DE 198 50 243 A1, owing to their highhydroxyl-containing reactive diluent content, have a comparatively highreactivity and, as a result, a comparatively short pot life orprocessing time.

[0008] European patent application EP 0 915 113 A1 discloses a curablecoating material comprising

[0009] (1a) a compound containing hydroxyl and carbamate groups,

[0010] (1b) a polyisocyanate crosslinking agent, and

[0011] (1c) an amino resin crosslinking agent.

[0012] Alternatively, the curable coating material comprises

[0013] (2a) a compound containing carbamate groups,

[0014] (2b) a compound containing hydroxyl groups,

[0015] (2c) a polyisocyanate crosslinking agent, and

[0016] (2d) an amino resin crosslinking agent.

[0017] In these materials it is essential that

[0018] the effective equivalents of the amino resin crosslinking agentare less than or equal to the equivalents of the carbamate groups, and

[0019] the effective equivalents of the polyisocyanate crosslinkingagent are less than or equal to the equivalents of the hydroxyl groups.

[0020] Preferably, the ratio of the effective equivalents of the aminoresin crosslinking agent to the effective equivalents of the carbamategroups is at least 0.6, more preferably at least 0.8.

[0021] The effect of this combination is that the viscosity in theinitial phase of crosslinking does not fall to such an extent thatexcessive flow of the coating material is accompanied by the developmentof surface defects, such as runs, depressions, “fat edges” or orangepeel.

[0022] This effect derives from the fact that the amino resincrosslinking agent reacts first with the carbamate groups before theblocked isocyanate groups of the polyisocyanate crosslinking agent reactwith the hydroxyl groups. The equivalents ratio has the consequence,moreover, that the amino resin crosslinking agent does not react withthe hydroxyl groups and so form unwanted ether groups which offer sitesfor attack by aggressive chemicals, such as acid rain, or actinicradiation, such as UV radiation.

[0023] Where polyisocyanate crosslinking agents containing freeisocyanate groups are used, they react with the hydroxyl groups beforethe amino resin crosslinking agent reacts with the carbamate groups, soproducing the same effect. Isocyanato-containing adducts such as areknown from the German patent application DE 196 09 617 A1 are not usedas polyisocyanate crosslinking agents.

[0024] The known coating material requires further improvement in itssolids content, and it is also necessary to increase further thecrosslinking density of the coatings produced from it.

[0025] The European patent application EP 0 710 707 A2 discloses acoating material which comprises a binder free of carbamate groups, acrosslinking agent, such as an amino resin or polyisocyanate, and a lowmolecular mass, oligomeric or polymeric constituent, particularly a lowmolecular mass constituent, that contains carbamate groups. The conjointuse of amino resins and polyisocyanates is not recommended in theEuropean patent application. Moreover, isocyanato-containing adductssuch as are known from the German patent application DE 196 09 617 A1are not used as polyisocyanate crosslinking agents. This known coatingmaterial as well requires further improvement in terms of its solidscontent, and it is also necessary to increase further the crosslinkingdensity of the coatings produced from it.

[0026] The German patent application DE 101 18 532.4, unpublished at thepriority date of the present specification, describes thermally curablemixtures comprising carbamate-functional binders and amino resincrosslinking agents. The known mixtures may further comprise additionalcrosslinking agents containing reactive functional groups which are ableto react with complementary reactive functional groups other thancarbamate groups, in particular with hydroxyl groups. Polyisocyanates,for example, may be used as additional crosslinking agents.Isocyanato-containing adducts such as are known from the German patentapplication DE 196 09 617 A1 are not used as polyisocyanate crosslinkingagents.

[0027] The German patent applications DE 100 21 139, DE 10020 969.6, andDE 100 23 229.9, which were unpublished at the priority date of thepresent specification, describe multicomponent coating materials,adhesives, and sealing compounds comprising binders andisocyanato-containing adducts such as are known from the German patentapplication DE 196 09 617 A1. The binders are (meth)acrylate copolymersbased on selected hydroxyl-containing (meth)acrylate monomers. Thebinders may also include in copolymerized form at least one furthermonomer, which may be selected from 14 monomer classes. Among others,monomers containing carbamate groups may also be used. Furthermore, thecoating materials, adhesives, and sealing compounds may also includeadditional crosslinking agents which may be selected from the groupconsisting of amino resins, compounds containing epoxide groups,compounds containing carboxyl groups, blocked polyisocyanates, andtris(alkoxycarbonylamino)triazines. Further, nonblocked polyisocyanatesas well may be used as reactive crosslinking agents. In the examples,however, only mixtures containing carbamate-free binders, adducts inaccordance with the German patent application DE 196 09 617 A1, andnonblocked polyisocyanates are described.

[0028] The German patent application DE 100 47 989.9, unpublished at thepriority date of the present specification, describes multicomponentcoating materials, adhesives, and sealing compounds which are curablethermally and with actinic radiation and which additionally comprise atleast one crosslinking agent containing on average per molecule at leastone isocyanate group and at least one functional group having at leastone bond which can be activated with actinic radiation.

[0029] Here and below, actinic radiation means electromagneticradiation, such as near infrared (NIR), visible light, UV radiation, andX-rays, especially UV radiation, and corpuscular radiation, such aselectron beams.

[0030] The German patent application DE 101 40 145.0, unpublished at thepriority date of the present specification, describes curablecompositions which comprise carbamate-functional constituents and alarge number of polyisocyanates as crosslinking agents. In this case itis possible, inter alia, to use, as polyisocyanates, the adducts knownfrom the German patent application DE 196 09 617 A1. In special cases,the curable compositions may comprise amino resins. Where they are used,they are present in amounts such that the crosslinking of the carbamategroups takes place primarily by way of the polyisocyanates. Theequivalents ratio of complementary reactive functional groups in theamino resins to the carbamate groups present is preferably not more than0.2.

[0031] It is an object of the present invention to provide a novelcurable composition which is easy to prepare, has a high solids content,and, as a two-component or multicomponent system, has a comparativelylong pot life or processing time. Where necessary, the novel curablecomposition should also be curable with actinic radiation.

[0032] The novel composition is to be highly suited to the production offilms and moldings and also very highly suited as a coating material,adhesive, and sealing compound for producing coatings, adhesive films,and seals. In particular, the novel coatings are to have theadvantageous properties associated with the known coatings based oncarbamate-functional binders, amino resins, and polyisocyanates, such asa particularly high weathering stability and etch resistance.Furthermore, however, they are to have a higher hardness and scratchresistance at the same time as a high acid resistance.

[0033] The invention accordingly provides the novel curable compositioncomprising

[0034] (A) at least one constituent containing at least two carbamategroups of the general formula I:

—O—C(O)—NHR (I)

[0035]  in which R is a hydrogen atom or a substituted or unsubstitutedalkyl, cycloalkyl or aryl group,

[0036] (B) at least one constituent containing carbamate-reactivefunctional groups selected from the group consisting of methylol,methoxyalkyl, N-methylol, and N-methoxyalkyl groups, the equivalentsratio of carbamate-reactive groups in (B) to carbamate groups in (A)being >0.2,

[0037] (C) at least one adduct preparable from

[0038] (c1) at least one polyisocyanate and

[0039] (c2) at least one compound of the general formula II containingan isocyanate-reactive functional group:

[0040]  in which the variables have the following meanings:

[0041] R¹ and R²: independently of one another=hydrogen atoms or alkylgroups having from 1 to 10 carbon atoms;

[0042] X and Y: independently of one another =oxygen atom, sulfur atomor a group >N—R⁶, in which R⁶=aliphatic group having from 1 to 30 carbonatoms, whose carbon chain may be interrupted by one or more oxygenatoms, or aromatic groups having from 6 to 30 carbon atoms;

[0043] R³: alkylene group having from 1 to 5 carbon atoms;

[0044] R⁴ and R⁵: independently of one another=hydrogen atoms,isocyanate-reactive functional groups or groups R⁶;

[0045] with the proviso that one group R⁴, R⁵ or R⁶ contains anisocyanate-reactive functional group or one group R⁴ or R⁵ is anisocyanate-reactive functional group and the other radicals R⁴, R⁵ orR⁶—where present—contain no isocyanate-reactive functional groups;

[0046] the molar ratio of polyisocyanates (c1) to compounds (c2) beingchosen such that the adducts (C) still contain on average per moleculeat least one free isocyanate group.

[0047] In the text below, the novel curable composition is referred toas the “composition of the invention”.

[0048] Further subject matter of the invention will emerge from thedescription.

[0049] In the light of the prior art it was surprising and unforeseeablefor the skilled worker that the object on which the present inventionwas based could be achieved by means of the composition of theinvention.

[0050] A particular surprise was that the composition of the inventioncould be prepared easily from commercial coating materials by adding thecompounds or adducts (C) for use in accordance with the invention andthat it had a comparatively long pot life or processing time and a highsolids.

[0051] In particular, it was surprising that the composition of theinvention was outstandingly suitable for producing moldings and films.

[0052] It was also surprising that the composition of the invention wasalso outstandingly suitable as a coating material, adhesive, and sealingcompound for producing coatings, adhesive films, and seals, preferablycoatings, especially electrocoats, surfacer coats, antistonechip primercoats, solid-color topcoats, basecoats, and clearcoats.

[0053] Surprisingly, the novel films, moldings, coatings, adhesivefilms, and seals were highly suitable for the coating, adhesive bonding,sealing, wrapping, and packaging of motor vehicle bodies and partsthereof, the inside and outside of buildings and parts thereof, doors,windows, furniture, hollow glassware, coils, containers, packaging,small parts, such as nuts and bolts, wheel rims or hub caps, electricalcomponents, such as wound goods (coils, stators, rotors), and componentsfor white goods, such as radiators, domestic appliances, refrigeratorcasings or washing machine casings.

[0054] The first essential constituent of the composition of theinvention is at least one constituent (A) containing at least two,preferably at least three and in particular at least four carbamategroups of the general formula I. In the general formula I the variable Ris a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkylor aryl group.

[0055] Suitable alkyl groups have from 1 to 20 carbon atoms. Examples ofsuitable alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl,secondary-butyl, isobutyl, tertiary-butyl, amyl, n-hexyl, heptyl, octyl,isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosanylgroups.

[0056] Suitable cycloalkyl groups are monocyclic, bicyclic, andpolycyclic cycloalkyl groups having from 5 to 20 carbon atoms. Thecycloalkyl groups are preferably selected from the group consisting ofsubstituted and unsubstituted cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.2.2]-octan-1-yl,decalin-1-yl, hydroindan-1-yl, dicyclopentanyl, tricyclodecan-1-yl,adamantan-1-yl, camphan-4-yl, pinan-4-yl, caran-1-yl, and norbornan-1-ylgroups.

[0057] Suitable aryl groups are monocyclic, bicyclic, and polycyclicaryl groups having from 6 to 20 carbon atoms. The aryl groups arepreferably selected from the group consisting of phenyl, naphthyl,biphenylyl, and phenanthrenyl groups.

[0058] Where used, the substituents are selected from the groupconsisting of halogen atoms, nitrile groups, nitro groups, partially orfully halogenated alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl,aryl, alkylaryl, cycloalkylaryl, arylalkyl, and arylcycloalkyl groups;aryloxy, alkyloxy, and cycloalkyloxy groups; and also arylthio,alkylthio, and cycloalkylthio groups; the alkyl, cycloalkyl, and arylgroups used being those described above.

[0059] Preferably, the alkyl, cycloalkyl, and aryl groups areunsubstituted. With particular preference, R is a hydrogen atom.

[0060] The constituent (A) may be of low molecular mass. Examples ofsuitable low molecular mass constituents (A) are described in detail inthe references

[0061] EP 0 710 707 A2, page 4 lines 1 to 27, or EP 0 915 113 A1, page 2lines 44 to 48 and page 6 lines 21 to 25,

[0062] EP 0 636 660 B1, column 1 line 41 to column 2 line 3, column 2line 12 to column 3 line 32, and column 5 line 43 to column 6 line 36,or

[0063] WO 87/00851, page 13 line 11 to page 15 line 8, and Example 1 toExample 33, pages 17 to 27.

[0064] These low molecular mass constituents (A) permit the preparationof particularly high-solids compositions of the invention.

[0065] The constituent (A) may be oligomeric and/or polymeric.

[0066] Suitable oligomers and polymers (A) come from the polymer classesof the random, alternating and/or block, linear and/or branched, and/orcomb, addition (co)polymers of ethylenically unsaturated monomers, orpolyaddition resins and/or polycondensation resins. For further detailsof these terms, refer to Römpp Lexikon Lacke und Druckfarben, GeorgThieme Verlag, Stuttgart, N.Y., 1998, page 457, “polyaddition” and“polyaddition resins (polyadducts)”, and also pages 463 and 464,“polycondensates”, “polycondensation”, and “polycondensation resins”.

[0067] Examples of highly suitable addition (co)polymers (A) are(meth)acrylate copolymers and partially hydrolyzed polyvinyl esters,especially (meth)acrylate copolymers.

[0068] Examples of highly suitable polyaddition resins and/orpolycondenstion resins (A) are polyesters, alkyds, polyurethanes,polylactones, polycarbonates, polyethers, epoxy resin-amine adducts,polyureas, polyamides or polyimides, especially polyesters.

[0069] With very particular preference, the oligomers and/or polymers(A) come from the polymer classes of the (meth)acrylate copolymers andpolyesters.

[0070] Carbamate-functional oligomers and polymers (A) which come fromthe abovementioned polymer classes, and processes for preparing them,are known from the patent applications

[0071] EP 0 594 068 A1, page 2 line 45 to page 4 line 27, page 5 lines36 to 57, and page 7 lines 1 to 22,

[0072] EP 0 594 142 A1, page 3 line 1 to page 4 line 37, page 5 line 49to page 6 line 12, and page 7 lines 5 to 26,

[0073] EP 0 675 141 B1, page 2 line 44 to page 5 line 15, and page 8line 5 to page 10 line 41,

[0074] WO 94/10211, page 4 line 18 to page 8 line 8, page 12 line 30 topage 14 line 36, page 15 line 35 to page 17 line 32, and page 18 line 16to page 19 line 30,

[0075] WO 01/23439, page 3 lines 13 to 29, page 4 line 25 to page 19line 18, in conjunction with the preparation examples 1 to 3, page 36line 16 to page 38 line 12, and

[0076] EP 0 915 113 A1, page 6 line 26 to page 8 line 49, and Example 1,page 11 lines 3 to 15.

[0077] The oligomers and/or polymers (A) are preferably prepared bycopolymerizing a monomer mixture comprising at least one olefinicallyunsaturated carboxylic acid, methacrylic acid for example, in thepresence of a glycidyl ester of Versatic® acid (cf. Römpp Lexikon Lackeund Druckfarben, Georg Thieme Verlag, Stuttgart N.Y., 1998, “Versatic®acids”, pages 605 and 606) and then reacting the resultanthydroxyl-containing (meth)acrylate copolymer with at least one alkylcarbamate, such as methyl, propyl or butyl carbamate. Or elsehydroxyl-containing (meth)acrylate copolymers and polyesters areconverted using phosgene into (meth)acrylate copolymers containingchloroformate groups, after which the chloroformate groups are convertedinto carbamate groups using ammonia or primary amines. It is alsopossible to react isocyanato-containing (meth)acrylate copolymers orpolyesters with at least one hydroxyalkyl carbamate, such as2-hydroxyethyl carbamate.

[0078] The oligomers and polymers (A) preferably have a number-averagemolecular weight of from 600 to 20,000, more preferably from 800 to15,000, with particular preference from 1000 to 10,000, with veryparticular preference from 1200 to 8000, and in particular from 1200 to6000 daltons.

[0079] Besides the carbamate groups, it is possible for the lowmolecular mass constituents, the oligomers and/or polymers (A) tocontain at least one, preferably at least two, and in particular atleast three reactive functional group(s) other than the carbamategroups. These reactive functional groups are preferably selected fromthe group consisting of isocyanate-reactive and non-isocyanate-reactivefunctional groups.

[0080] Examples of suitable isocyanate-reactive functional groups arehydroxyl, thiol, and primary and secondary amino groups, particularlyhydroxyl groups.

[0081] By non-isocyanate-reactive functional groups are meant thosegroups which react very little if at all with blocked and nonblockedisocyanate groups that are present, under the customary and knownconditions of thermal crosslinking. Examples of suitablenon-isocyanate-reactive groups are carboxyl groups, epoxide groups, andcyclic carbonate groups, particularly carboxyl groups.

[0082] With particular preference, hydroxyl groups are used.

[0083] Examples of suitable low molecular mass constituents (A)containing hydroxyl groups are known from European patent application EP0 915 113 A1, page 6 lines 21 to 25, or the international patentapplication WO 87/00851, page 13 line 11 to page 15 line 8, and Example1 to Example 33, pages 17 to 27.

[0084] Examples of suitable oligomeric and polymeric constituents (A)which contain hydroxyl groups are known from the European patentapplication EP 0 915 113 A1, Example 1, page 11 lines 3 to 15, and fromthe European patent EP 0 675 141 B1, page 2 line 44 to page 5 line 15and page 8 line 5 to page 10 line 41.

[0085] Where the constituents (A) contain reactive functional groupsother than the carbamate groups, they are preferably present in minoramounts, so that the compositions of the invention are crosslinkedprimarily by way of the carbamate groups. By a minor amount is meant anamount of the non-carbamate reactive functional groups in theconstituents (A) of <50, preferably <45, more preferably <40, withparticular preference <35, with very particular preference <30, and inparticular <25 equivalent %, based in each case on the total amount ofthe reactive functional groups in a constituent (A).

[0086] The amount of the above-described compounds (A) in thecompositions of the invention may vary widely and is guided by therequirements of the case in hand, in particular by the functionality ofthe complementary reactive groups in the compounds (A) on the one handand in the crosslinking agents (B) and the adducts (C) on the other. Theamount is preferably from 20 to 80%, more preferably from 22 to 75%,with particular preference from 25 to 70%, with very particularpreference from 25 to 65%, and in particular form 25 to 60% by weight,based in each case on the solids of the composition of the invention.

[0087] The further essential constituent of the composition of theinvention is at least one constituent (B) containing carbamate-reactivefunctional groups selected from the group consisting of methylol,methoxyalkyl, N-methylol, and N-methyoxyalkyl groups. The constituents(B) are preferably amino resins, especially melamine resins. Examples ofsuitable amino resins are described in Römpp Lexikon Lacke undDruckfarben, Georg Thieme Verlag, 1998, page 29, “amino resins”, in thetext book “Lackadditive” [Additives for coatings] by Johan Bieleman,Wiley-VCH, Weinheim, N.Y., 1998, pages 242 ff., in the book “Paints,coatings and solvents”, second, completely revised edition, edited by D.Stoye and W. Freitag, Wiley-VCH, Weinheim, N.Y., 1998, pages 80 ff., inthe patents U.S. Pat. No. 4,710,542 A1 or EP 0 245 700 A1, and in thearticle by B. Singh and coworkers, “Carbamylmethylated melamines, novelcrosslinkers for the coatings industry” in Advanced Organic CoatingsScience and Technology Series, 1991, Volume 13, pages 193 to 207.

[0088] In the compositions of the invention, the constituents (B) arepresent in an amount such as to give an equivalents ratio ofcarbamate-reactive groups in (B) to carbamate groups in (A) of >0.2.

[0089] The further essential constituent of the composition of theinvention is at least one adduct (C) preparable from

[0090] (c1) at least one polyisocyanate, in particular a diisocyanate,and

[0091] (c2) at least one compound of the general formula II containingan isocyanate-reactive functional group:

[0092] in which the variables have the following meanings:

[0093] R¹ and R²: independently of one another=hydrogen atoms or alkylgroups having from 1 to 10 carbon atoms;

[0094] X and Y: independently of one another=oxygen atom, sulfur atom ora group >N—R⁶, in which R⁶=aliphatic group having from 1 to 30 carbonatoms, whose carbon chain may be interrupted by one or more oxygenatoms, or aromatic groups having from 6 to 30 carbon atoms;

[0095] R³: alkylene group having from 1 to 5 carbon atoms;

[0096] R⁴ and R⁵: independently of one another=hydrogen atoms,isocyanate-reactive functional groups or groups R⁶;

[0097] with the proviso that one group R⁴, R⁵ or R⁶ contains anisocyanate-reactive functional group or one group R⁴ or R⁵ is anisocyanate-reactive functional group and the other radicals R⁴, R⁵ or R⁶—where present—contain no isocyanate-reactive functional groups;

[0098] the molar ratio of polyisocyanates, especially diisocyanates,(c1) to compounds (c2) being chosen such that the adducts (C) stillcontain on average per molecule at least one free isocyanate group.

[0099] Examples of suitable polyisocyanates and diisocyanates are knownfrom the German patent applications DE 199 24 170 A1, column 2 lines 6to 34 in conjunction with column 3 line 61 to column 6 line 68, andcolumn 10 line 57 to column 11 line 38, DE 19947523 A1, page 7 line 56,page 8, page 13, or DE 199 30 067 A1, page 9 line 53 to page 10 line 6.

[0100] The compounds (c2) contain an isocyanate-reactive functionalgroup. Examples of suitable isocyanate-reactive functional groups arehydroxyl groups, thiol groups, and primary or secondary amino groups.

[0101] In the general formula II, R¹ and R² independently of one anotherare hydrogen atoms or alkyl groups having from 1 to 10 carbon atoms,preferably methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, n-pentyl, isoamyl, n-hexyl, n-heptyl, n-octyl,2-ethylhex-1-yl, n-nonyl or n-decyl groups, particularly isopropylgroups;

[0102] X and Y independently of one another are oxygen atoms, sulfuratoms or groups >N—R⁶, in which R⁶ is an aliphatic group having from 1to 30 carbon atoms, whose carbon chain may be interrupted by one or moreoxygen atoms, such as the above-described groups R¹ and R², undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl or eicosanyl or oligo(ethylene glycol)-1-yl,oligo(propylene glycol)-1-yl or oligo(butylene glycol)-1-yl groups, orthe corresponding mixed oligomers with a degree of oligomerization of upto 15. Additionally, R⁶ may be an aromatic group having from 6 to 30carbon atoms such as phenyl, naphthyl, biphenyl-1-yl or phenanthrenylgroups.

[0103] R³ is an alkylene group having from 1 to 5 carbon atoms such asmethylene, eth-1,2-ylene, trimethylene, tetramethylene or pentamethylenegroups. R⁴ and R⁵ independently of one another are hydrogen atoms,isocyanate-reactive functional groups or groups R⁶.

[0104] For the compounds (c2) it is essential that one group R⁴, R⁵ orR⁶ contains an isocyanate-reactive functional group or one group R⁴ orR⁵ is an isocyanate-reactive functional group, and the other groups R⁴,R⁵ or R⁶—where present—contain no isocyanate-reactive functional groups.

[0105] Examples of highly suitable compounds (c2) are dioxolanes of thegeneral formula III:

[0106] dioxanes of the general formula IV:

[0107] oxazolidines of the general formula V:

[0108] in which the groups R¹, R², R⁴, R⁵ and R⁶ are as defined above,the groups R⁴ or R⁶ containing an isocyanate-reactive functional group.

[0109] Examples of suitable dioxolanes (II), dioxanes (III), anddioxazolidines (IV), and their preparation, are described in detail inthe examples of the German patent application DE 196 09 617 A1, page 5line 54 to page 9 line 27.

[0110] Of these, the oxazolidines (IV) have particular advantages and soare used with particular preference in accordance with the invention.Examples of especially suitable oxazolidines (IV) areN-(2-hydroxyethyl)-1,3-oxazolidine orN-(2-hyeroxyethyl)-2-isopropyl-1,3-oxazolidine, as described on page 6,Table 1, No. 5a and No. 5b of the German patent application DE 196 09617 A1.

[0111] For the preparation of the adduct (C), the molar ratio ofpolyisocyanates, especially diisocyanates, (c1) to compounds (c2) ischosen so that the adducts (C) still contain on average per molecule atleast one free isocyanate group. The method of preparing the adducts (C)has no special features but is instead carried out as described in theGerman patent application DE 196 09 617 A1.

[0112] The amount of the above-described adducts (C) in the compositionsof the invention may vary very widely. It is guided in particular by thefunctionality of the constituents (A) and (B) and by the targetviscosity of the compositions of the invention. The amount is preferablyfrom 20 to 90%, more preferably from 22 to 85%, with particularpreference from 23 to 80%, with very particular preference from 24 to75%, and in particular from 25 to 70% by weight, based in each case onthe solids of the composition of the invention.

[0113] The composition of the invention may further comprise at leastone customary and known additive (D) selected from the group consistingof binders which cure physically, thermally, with actinic radiation, andthermally and with actinic radiation, and which are different thanabove-described binders (A); additional crosslinking agents; reactivediluents which are curable thermally, with actinic radiation, andthermally and with actinic radiation; photoinitiators; molecularlydispersely soluble dyes; light stabilizers, such as UV absorbers andreversible free-radical scavengers (HALS); antioxidants; low-boiling andhigh-boiling (“long”) organic solvents; devolatilizers; wetting agents;emulsifiers; slip additives; polymerization inhibitors; thermalcrosslinking catalysts; thermolabile free-radical initiators; adhesionpromoters; leveling agents; film formation auxiliaries; rheologicalaids, such as thickeners and pseudoplastic sag control agents, SCAs;flame retardants; corrosion inhibitors; free-flow aids; waxes;siccatives; biocides; and flatting agents.

[0114] Examples of suitable additives are described in detail in thetextbook “Lackadditive” by Johan Bieleman, Weinheim VCH, Weinheim, N.Y.,1998, in D. Stoye and W. Freitag (editors) “Paints, coatings andsolvents”, second, completely revised edition, Wiley-VCH, Weinheim,N.Y., 1998, “14.9. solvent groups”, pages 327 to 373 in the Germanpatent application DE 199 14 896 A1, column 14 line 26 to column 15 line46, or in the German patent application DE 199 08 018 A1, page 9 line 31to page 8 line 30. For further details, refer to the German patentapplications DE 199 04 317 A1, DE 198 18 735 A1, and DE 198 55 125 A1 orto the German patent DE 197 09 476 C1.

[0115] The compositions of the invention comprising the constituentsdescribed above are used in particular as clearcoat materials forproducing clearcoats or as starting products for producing clear,transparent films and moldings.

[0116] Alternatively, the compositions of the invention may bepigmented. In that case they preferably comprise at least one pigment(E) selected from the group consisting of organic and inorganic,transparent and opaque, color and/or effect, electrically conductive,magnetically shielding, and fluorescent pigments, fillers, andnanoparticles.

[0117] The pigmented compositions of the invention are used inparticular as electrocoat materials, surfacers, basecoat materials, andsolid-color topcoat materials for producing electrocoats, surfacer coatsor antistonechip primer coats, basecoats and solid-color topcoats, orfor producing pigmented films and moldings.

[0118] Where exclusively non-opaque, transparent pigments are used,particularly nanoparticles, the pigmented compositions of the inventionmay also be used as clearcoat materials or for producing clear,transparent films and moldings.

[0119] In terms of its method, the preparation of the composition of theinvention has no special features but instead takes place by the mixingand homogenizing of the above-described constituents with the aid ofcustomary and known mixing techniques and apparatus such as stirredtanks, stirred mills, extruders, compounders, Ultraturrax, inlinedissolvers, static mixers, micromixers, toothed-ring dispersers,pressure relief nozzles and/or microfluidizers, in the absence whereappropriate of actinic radiation. It is an advantage to prepare a stockvarnish from the constituents (A) and (B) and also, where appropriate,the constituents (D) and/or (E), to which the adduct (C) is then addedprior to the application of the composition of the invention.

[0120] The resulting compositions of the invention are conventionalcompositions, containing organic solvents, aqueous compositions,substantially or completely solvent-free and water-free liquidcompositions (100% systems), substantially or completely solvent-freeand water-free solid powders, or substantially or completelysolvent-free powder suspensions (powder slurries).

[0121] The compositions of the invention are applied to customary andknown, temporary or permanent substrates. For the production of filmsand moldings of the invention it is preferred to use customary and knowntemporary substrates, such as metal and polymer belts or hollow bodiesmade of metal, glass, plastic, wood or ceramic which can be removedeasily without damaging the films and moldings of the invention. Wherethe compositions of the invention are used to produce coatings,adhesives, films and seals, permosubstrates are used, such as motorvehicle bodies and parts thereof, the inside and outside of buildingsand parts thereof, doors, is windows, furniture, hollow glassware,coils, containers, packaging, small parts, electrical components, andcomponents for white goods. The films and moldings of the invention maylikewise serve as substrates. Further examples of suitable substratesare known from the German patent applications DE 199 24 172 A1, page 8lines 21 to 37, or DE 199 30 067 A1, page 13 line 61 to page 14 line 16.

[0122] In terms of its method, the application of the compositions ofthe invention has no special features but may instead take place by anycustomary and known application method suitable for the composition inquestion, examples being electrodeposition, spraying, squirting,knifecoating, brushing, flowcoating, dipping, trickling or rolling.Preference is given to using spray application methods, except where thecomposition is a powder.

[0123] The application of the powders also has no special features asfar as its method is concerned but instead takes place, for example, bythe customary and known fluidized bed techniques, such as are known, forexample, from the BASF Coatings AG brochures “Pulverlacke fürindustrielle Anwendungen” [Powder coating materials for industrialapplications], January 2000, or “Coatings Partner, Pulverlack Spezial”[Coatings partner, powder coatings special], {fraction (1/2000)}, orRömpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart,N.Y., 1998, pages 187 and 188, “electrostatic powder spraying”,“electrostatic spraying”, and “electrostatic fluidized bath process”.

[0124] The compositions of the invention are used preferably to producemoldings and films or as coating materials, adhesives, and sealingcompounds for producing coatings, adhesive films, and seals. Inparticular the coating materials are used to produce multicoat colorand/or effect paint systems by the customary and known wet-on-wettechniques (cf., for example, the German patent applications DE 199 14896 A1, column 16 line 54 to column 18 line 57, or DE 199 30 067 A1,page 15 line 25 to page 16 line 36).

[0125] The curing of the applied compositions of the invention also hasno special features in terms of its method and instead takes place withthe aid of the customary and known thermal methods, such as heating in aforced air oven or irradiation with IR lamps, and also, whereappropriate, with the aid of the customary and known methods ofradiation curing, as are described, for example, in the German patentapplication DE 198 18 735 A1, column 10 line 31 to column 11 line 33.

[0126] The resultant coatings and films of the invention, especially thesingle-coat or multicoat color and/or effect paint systems andclearcoats of the invention, particularly the clearcoats, are easy toproduce and have outstanding optical properties and very high lightstability, chemical resistance, water resistance, condensationresistance, weathering stability, and etch resistance. In particular,they are free from turbidities and inhomogeneities. They exhibitoutstanding scratch resistance and abrasion resistance combined with anoutstanding surface hardness and acid resistance.

[0127] The adhesive films of the invention permanently and firmly join avery wide variety of substrates to one another and possess high chemicaland mechanical stability even in the case of extreme temperatures and/ortemperature fluctuations.

[0128] Similarly, the seals of the invention seal the substratespermanently, and exhibit high mechanical and chemical stability even inthe case of extreme temperatures and/or temperature fluctuations, andeven in conjunction with exposure to aggressive chemicals.

[0129] Accordingly, the primed or unprimed substrates commonly employedin the technological fields recited above and coated with at least onecoating of the invention, bonded with at least one adhesive film of theinvention, sealed with at least one seal of the invention and/or wrappedor packaged with at least one film of the invention or at least onemolding of the invention combine a particularly advantageous profile ofperformance properties with a particularly long service life, so makingthem particularly attractive both economically and environmentally.

EXAMPLES Preparation Example 1

[0130] The Preparation of a Methacrylate Copolymer (A) ContainingCarbamate Groups

[0131] A reactor equipped with a stirrer, oil heating, two droppingfunnels, a nitrogen inlet pipe, a thermometer, and a reflux condenserwas charged with 326.1 parts by weight of methyl carbamate, 489.8 partsby weight of xylene and 482.6 parts by weight of Cardura® E 10 (glycidylester of Versatic® acid from Shell) and this initial charge is heated to140° C. with stirring. After it has reached this temperature, a monomermixture of 434.6 parts by weight of hydroxymethyl methacrylate, 119parts by weight of styrene and 163.6 parts by weight of methacrylic acidwas metered into the initial charge at a uniform rate over the course ofthree hours and an initiator solution of 72 parts by weight of Vazo® 67(2,2′-azobis(2-methylbutanenitrile) from Du Pont) and 181.9 parts byweight of xylene was metered into the initial charge at a uniform rateover the course of three hours. The two feeds were commencedsimultaneously. After the end of the feeds, the reaction mixture wascooled to 115° C. over the course of 30 minutes. Then an initiatorsolution of 12.1 parts by weight of 2,2′-azobis(2-methylbutanenitrile)and 36.9 parts by weight of xylene was metered into the reaction mixtureover the course of one hour, after which the reaction mixture was heldat 115° C. for a further hour. Following the addition of 2.8 parts byweight of Fascat® 4100 (monobutyltin oxide from Atochem) in 31.3 partsby weight of cyclohexane, the reaction mixture was heated to 140° C.with stirring and held at this temperature until the hydroxyl number was77 mg KOH/g solids. The reaction mixture was subsequently cooled to 100°C. and diluted with 25 parts by weight of methyl isobutyl ketone and 125parts by weight of xylene. Unreacted methyl carbamate and thecyclohexane were distilled off under reduced pressure at 130° C. untilthe methyl carbamate content was <2% by weight. After cooling to 80° C.,the reaction mixture was diluted with 125 parts by weight ofmethoxypropanol. The resulting solution of the carbamate-functionalmethacrylate copolymer (A) had a solids content of 70% by weight (60minutes forced air oven/130° C.), an acid number of from 1 to 4 mg KOH/gsolids, and a color number of from 4 to 5 (Gardner).

Preparation Example 2

[0132] The Preparation of the Solution of a Thixotropic Agent (D)

[0133] In a reactor, 814 parts by weight of the methacrylate copolymersolution (A) from Preparation Example 1 were mixed with 96 parts byweight of Solventnaphtha® and 19.6 parts by weight of benzylamine. Withvigorous stirring, a mixture of 15.4 parts by weight of hexamethylenediisocyanate and 35 parts by weight of Solventnaphtha® was added. Theresulting reaction mixture was stirred for 15 minutes more. The solutionof the thixotropic agent (D) had a solids content of 60% by weight (60minutes forced air oven/130° C.).

Preparation Example 3

[0134] The Preparation of a Thixotroping Paste (D)

[0135] In a stirred laboratory mill from Vollrath, 800 g of millbaseconsisting of 592 parts by weight of the methacrylate copolymer solution(A) from Preparation Example 1, 80 parts by weight of butyl acetate, 64parts by weight of xylene and 64 parts by weight of Aerosil® 972(average primary particle size: 16 nm; internal surface area by BET inaccordance with DIN 66131: 110±20 m²/g; Degussa A G, Hanau, Germany)were weighed out together with 1100 parts by weight of quartz sand(grain size 0.7-1 mm) and this millbase was dispersed for 30 minuteswith water cooling. The quartz sand was then separated off.

Preparation Example 4

[0136] The Preparation of a Blocked Polyisocyanate (AdditionalCrosslinking Agent (D))

[0137] In a suitable stainless steel reactor, 40 parts by weight ofBasonat® HI 190 B/S (hexamethylene diisocyanate-based isocyanate fromBASF Aktiengesellschaft) and 16.4 parts by weight of Solventnaphthagwere weighed out and heated to 50° C. Over the course of four hours,26.27 parts by weight of diethyl malonate, 6.5 parts by weight of ethylacetoacetate and 0.3 part by weight of catalyst solution (sodiummethylhexanoate) were metered in at a uniform rate. Thereafter thetemperature was raised to 70° C. When an isocyanate equivalent weight offrom 5900 to 6800 had been reached, 1.03 parts by weight of1,4-cyclohexanedimethanol were added at 70° C. over the course of 30minutes with stirring. When an isocyanate equivalent weight of ≧13,000had been reached, 5 parts by weight of n-butanol were added. Thetemperature of the reaction mixture was lowered to 50° C. and theresulting blocked polyisocyanate was diluted with n-butanol to atheoretical solids content of 68% by weight.

Examples 1 and 2

[0138] The Preparation of the Inventive Clearcoat Materials 1 and 2

[0139] To prepare the inventive clearcoat materials 1 and 2, first ofall a stock varnish was prepared by mixing and homogenizing thefollowing constituents:

[0140] 206 parts by weight of the methacrylate copolymer solution (A)from Preparation Example 1,

[0141] 207 parts by weight of the solution of thixotropic agent (D) fromPreparation Example 2,

[0142] 41 parts by weight of the thixotroping paste (D) from PreparationExample 3,

[0143] 55 parts by weight of the blocked polyisocyanate (D) fromPreparation Example 4,

[0144] 5 parts by weight of Disperbyk® 161 (30 percent solution of acommercial wetting agent from Byk Chemie),

[0145] 128 parts by weight of Resimene® BM-9539 (constituent (B);commercial, methyl- and butyl-etherified melamine resin from Monsanto),

[0146] 10 parts by weight of Tinuvin® 384 (commercial UV absorber fromCiba Specialty Chemicals, Inc.),

[0147] 8 parts by weight of Tinuvin® 123 (commercial reversiblefree-radical scavenger, sterically hindered amine (HALS) from CibaSpecialty Chemicals, Inc.),

[0148] 20 parts by weight of Nacure® 5528 (commercial catalyst(amine-blocked sulfonic acid derivative) from King),

[0149] 2 parts by weight of Silwet® L-7604 (commercial additive fromWitco Surfactants),

[0150] 31 parts by weight of butyl diglycol acetate,

[0151] 37 parts by weight of xylene,

[0152] 47 parts by weight of Solvesso® 200,

[0153] 153 parts by weight of Solventnaphtha, and

[0154] 31 parts by weight of butyl glycolate.

[0155] The stock varnish was adjusted using Solventnaphta® II to a sprayviscosity of 26 seconds in a DIN 4 flow cup. The varnish then had asolids content of 43.3% by weight (1 hour/125° C.).

Example 1

[0156] To prepare the inventive clearcoat material 1, 100 parts byweight of the stock varnish were admixed with 30 parts by weight ofBasonat® SCI 3000 mPas from BASF Aktiengesellschaft (adduct (C) of 1 molof the allophanate of hexamethylene diisocyanate and 1 mol ofN-(2-hydroxyethyl)-2-isopropyloxazolidine) and adjusted usingSolventnaphta® II to a spray viscosity of 26 seconds in a DIN 4 flowcup. The inventive clearcoat material 1 then had a solids content of53.7% by weight (1 hour/125° C.).

Example 2

[0157] To prepare the inventive clearcoat material 2, Example 1 wasrepeated but using 50 parts by weight rather than 30 parts by weight ofBasonat® SCI 3000 mPas. The inventive clearcoat material 2 had a solidscontent of 57.3% by weight (1 hour/125° C.).

[0158] The inventive clearcoat materials were outstandingly suitable forthe production of clearcoats and of multicoat color and/or effect paintsystems by the wet-on-wet technique. They could be used to produce bothoriginal finishes and refinishes.

Examples 3 and 4

[0159] The Production of the Inventive Color Multicoat Paint Systems 1and 2

[0160] To produce the multicoat paint systems 1 and 2, steel test panelswhich have been coated with an electrocoat in a dry film thickness offrom 18 to 22 μm were coated with a waterborne surfacer. The resultingwaterborne surfacer film was baked at 160° C. for 20 minutes so as togive a surfacer coat with a dry film thickness of from 35 to 40 μm. Thesurfacer coat was subsequently coated with a black aqueous basecoatmaterial from BASF Coatings AG in a film thickness from 12 to 15 μm. Theresulting aqueous basecoat films were flashed off at 80° C. for 10minutes. Thereafter, the clearcoat material 1 from Example 3 and theclearcoat material 2 from Example 4 were each applied pneumaticallyusing a gravity-feed cup gun in one cross pass in a film thickness offrom 40 to 45 μm. The clearcoat films were subsequently flashed off atroom temperature for 10 minutes and at 80° C. for 10 minutes andtogether with the aqueous basecoat films were baked in a forced air ovenat 140° C. for 20 minutes. This gave the inventive multicoat color paintsystems 1 and 2.

[0161] These systems were of “automotive quality” (cf. also the Europeanpatent EP 0 352 298 B1 in this respect, page 15 line 42 to page 17 line40) as regards gloss, distinctness of image, uniformity of hiding power,uniformity of film thickness, resistance to fuel, solvents, and acids,hardness, abrasion resistance, scratch resistance, impact strength,adhesion, weathering stability, and resistance to water and moisture.They were therefore also suitable for use in the finishing of top-classautomobiles.

1. A curable composition comprising (a) at least one constituentcontaining at least two carbamate groups of the general formula I:—O—C(O)—NHR(I)  in which R is a hydrogen atom or a substituted orunsubstituted alkyl group, a substituted or unsubstituted cycloalkylgroup, or a substituted or unsubstituted aryl group, (B) at least oneconstituent containing carbamate-reactive functional groups selectedfrom the group consisting of methylol, methoxyalkyl, N-methylol,N-methoxyalkyl groups, and combinations thereof, an equivalents ratio ofcarbamate-reactive groups in (B) to carbamate groups in (A) being >0.2,(C) at least one adduct comprising a reaction product of (c1) at leastone polyisocyanate and (c2) at least one compound of the general formulaII containing an isocyanate-reactive functional group:

 wherein R¹ and R²: independently of one another =hydrogen atoms oralkyl groups having from 1 to 10 carbon atoms; X and Y: independently ofone another =oxygen atom, sulfur atom or a group >N—R⁶, in whichR⁶=aliphatic group having from 1 to 30 carbon atoms, whose carbon chainmay be interrupted by one or more oxygen atoms, or aromatic groupshaving from 6 to 30 carbon atoms; R³: alkylene group having from 1 to 5carbon atoms; R⁴ and R⁵: independently of one another=hydrogen atoms,isocyanate-reactive functional groups or groups R⁶; with the provisothat one group R⁴, R⁵, or R⁶ contains an isocyanate-reactive functionalgroup or one group R⁴ or R⁵ is an isocyanate-reactive functional groupand the other radicals R⁴, R⁵, or R⁶—where present—contain noisocyanate-reactive functional groups; the molar ratio ofpolyisocyanates (c1) to compounds (c2) being chosen such that theadducts (C) still contain on average per molecule at least one freeisocyanate group.
 2. The curable composition of claim 1, wherein thecompounds of the general formula II comprise at least one of dioxolanesof the general formula III:

dioxanes of the general formula IV:

or oxazolidines of the general formula V:

in which the groups R¹, R², R⁴, R⁵ and R⁶ are as defined above, thegroups R⁴ or R⁶ containing an isocyanate-reactive functional group. 3.The curable composition of claim 1, wherein the isocyanate-reactivefunctional groups are selected from the group consisting of hydroxyl,thiol, primary amino groups, secondary amino groups, and combinationsthereof.
 4. The curable composition of claim 1, wherein the constituents(A) are (meth)acrylate copolymers.
 5. The curable composition of claim1, wherein the constituents (B) are amino resins.
 6. The curablecomposition of claim 1, further comprising at least one of at least oneadditive (D) and/or at least one pigment (E).
 7. The curable compositionof claim 6, wherein the additive (D) is selected from the groupconsisting of a binders that cures by one of physically, thermally, withactinic radiation, or thermally and with actinic radiation, and which isdifferent than the constituents (A); an additional crosslinking agents;a reactive diluents that is curable by one of thermally, with actinicradiation, or thermally and with actinic radiation; a photoinitiators; amolecularly dispersely soluble dye; a light stabilizers; a UV absorbers;a reversible free-radical scavengers; an antioxidants; an organicsolvent; a devolatilizer; a wetting agent; an emulsifier; a slipadditive; polymerization inhibitor; a thermal crosslinking catalyst; athermolabile free-radical initiator; an adhesion promoter; a levelingagents; a film formation auxiliary; a rheological aid; a thickener; apseudoplastic sag control agent; a flame retardant; a corrosioninhibitor; a free-flow aid; a wax; a siccative; a biocide; a flattingagent, and combinations thereof.
 8. The curable composition of claim 6,wherein the pigment (E) is selected from the group consisting of organicpigments, inorganic pigments, transparent pigments, opaque pigments,color and/or effect pigments, electrically conductive pigments,magnetically shielding pigments, fluorescent pigments, fillers,nanoparticles and combinations thereof.
 9. The curable composition ofclaim 1, wherein the curable composition is one of an aqueouscomposition, a solvent-free and water-free composition, a solvent-freeand water-free solid powder, or a solvent-free powder suspension (powderslurry).
 10. A process for preparing the curable composition claim 1comprising (1) preparing a stock varnish from the constituents (A) and(B) and, optionally at least one of at least one additive (D) and/or atleast one pigment (E), and (2) mixing the adduct (C) with the stockvarnish.
 11. A method comprising applying the curable composition ofclaim 1 to a substrate and forming one of a coating, an adhesive film,or a seal.
 12. The method of claim 11, wherein the curable compositionfor each coating is a coating material selected from the groupconsisting of electrocoat materials, surfacers, antistonechip primers,solid-color topcoat materials, basecoat materials, and clearcoatmaterials.
 13. The method of claim 12, wherein the coating is amulticoat color and/or effect paint systems and the forming is awet-on-wet technique.
 14. The method of claim 11, wherein the substrateis one of a motor vehicle body, a motor vehicle part, a building, adoor, a window, furniture, hollow glassware, a coil, a container, apackaging, a part, an electrical component, or a white good.